DE2346734A1 - POLYESTER FIBERS THAT CAN BE DYED WITH ACID DYES - Google Patents

Description

Polyester fibers that can be dyed with acid dyes

The invention relates to improvements in the dyeing of polyester fibers and threads. In particular, the invention relates to textile fibers and threads made from linear terephthalic acid polyesters, which are suitable for dyeing in an acidic environment.

Polyester fibers are difficult to dye. Such fibers To make it receptive to basic and acidic dyes, it was previously necessary to place dye-receptive sites in the polyester molecules to store. The USA patent specification 3,018,272 describes a process which has been a considerable technical success has had to modify polyesters in order for basic To obtain dyestuffs-sensitive polymers. The previously known methods for the production of modified polyesters, however, those susceptible to acid dyes have been general not so successful. There has long been a need in the textile industry for polyester fibers that can be easily stained with acid dyes.

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US Pat. No. 2,647,104 discloses that chemically modified polyethylene terephthalate, which is sufficiently basic Contains nitrogen in order to be dyeable with acid dyes and with direct dyes, can be prepared by Polyethylene terephthalate with N-alkyl-substituted diethanolamines and similar amino alcohols.

U.S. Patent 3,624,181 discloses that polyester fibers can be imparted dyeability with acid dyes can by modifying polyethylene terephthalate with a glycol having a tertiary amino group, which the general formula

w c-Ii- dialkyl ² \

H (OCH ₂ CH ₂ ) OCH ₂ C CH ₂ O (CH ₂ CH ₂ O) _q H

Alkyl

in which ρ and q can have values from 0 to 10. According to the example 1 of the patent mentioned is dimethyl terephthalate with a glycol of the general formula

HQH ₂ CcCH ₂ OH

CH ₂ !

implemented. Example 8 then becomes the reaction product of example 1 in the melt with polyethylene terephthalate / isophthalate (copolyester from 90% ethylene terephthalate units and 10% Ethylene isophthalate units) mixed and processed into fibers, which are then dyed according to Example 14 with acid dyes. These polyester fibers have in their molecules basic nitrogen sites located in piperidine rings

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and are bound to the polyester molecule via alkylene groups. According to example 15 of the patent mentioned becomes a tertiary amine of the general formula

H (OCH ₂ CH ₂₎ OCH ₂ -C-CH ₂ O (CH ₂ CH ₂ O) q H

(in which the mean value of ρ + q = 3) so into a terephthalic acid polyester incorporated that the basic nitrogen site in the molecule is localized in a tertiary amine and attached to the terephthalic acid polyester is bound via a methylene group and short oxyethylene bonds.

Although in these and other publications ways and means are disclosed to impart dyeability with acid dyes to polyester fibers and threads / are the known methods often accompanied by one or more of the following disadvantages: If the modifier in the known methods in sufficient Amount is incorporated in order to achieve a good subsequent uptake of the acid dye, the amount of the same is often so large that the polymer is impaired. Namely, some of the modifiers cause discoloration of terephthalic acid polyester. Other modifiers are not stable enough to prevent discoloration of the polyester, when heated to the elevated temperatures required for polymerization and melt spinning are. Some modifiers tend to limit the length of the polyester molecules during polymerization. Some of the modified polyesters require strongly acidic conditions, e.g. pH values below 3, in order to achieve satisfactory colorations.

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However, it is desirable to conduct coloring under less acidic conditions to make the occurrence more disadvantageous Avoid effects when the fibers dyed with acid dyes together with cellulose fibers or with basic dyeable polyester fibers, as described in US Pat. No. 3,018,272, can be processed into yarns. Furthermore, the polyesters modified in the manner known hitherto show under the less strongly acidic conditions that are particularly desirable for mixed fiber yarns, often only a low absorption capacity for acid dyes.

To some or all of these as well as other disadvantages of the stand To eliminate or at least to reduce the technology, the invention provides textile fibers dyable with acid dyes and threads made of a linear terephthalic acid polyester, in which the polyester molecules are basic Piperidine groups are bonded, and is characterized by the fact that 2,2,6,6-tetramethylpiperidine groups are attached to the polyester molecules directly at their positions no. 1 and / or no. 4 or via oxyalkylene, alkylene, aromatic amide or amino-s-triazine groups are bonded.

Furthermore, the invention provides a method for dyeing textile fibers or threads made of a linear terephthalic acid polyester, in which basic piperidine groups are bound to the polyester molecules, with acid dyes available, which is characterized in that the piperidine groups are 2,2,6,6-tetramethylpiperidine groups and the fibers or Threads are dyed from an acidic dye liquor. Usually the pH is at least 3 and less than 6, especially 3.5 to 5.0.

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The linear terephthalic acid polyester fibers according to the invention have a strong affinity for acid dyes a basic nitrogen atom located in a 2,2,6,6-tetramethylpiperidine group which is bound to the polyester molecules directly or via a bond of a special kind is. According to a particular embodiment of the invention, the nitrogen atom is in a 1-low. Alkyl-2,2-, 6,6-tetramethylpiper.idine group, with a 1,2,2,6,6-pentamethylpiperidine group being preferred. If these piperidine groups in the For the purposes of the invention are bound to polyester molecules, this results in pasers which can be dyed with acid dyes and which Surprisingly, do not suffer any undesirable discoloration. It is believed that this favorable outcome at least is based in part on the fact that (1) the piperidine nitrogen atom is strongly basic, so that strong interactions between Acid dyes and the polymer come about, and (2) the piperidine ring has four methyl substituents which During polymerization or melting, reactive centers come closer together, causing the polyester to degrade (e.g. discoloration or quarternization reactions).

For the purposes of the invention the concentration of basic is Nitrogen (i.e. in the piperidine ring) generally 0.02 to 0.25, preferably 0.05 to 0.15, weight percent based on the weight of the dyeable, modified, with acid dyes, linear terephthalic acid polyester. The nitrogen-containing, modifying group is preferably not at the end, but inside the polyester molecular chain. Modifier molecules that change under the conditions under which the modified Polyester produced according to the invention, only bind to the ends of the polyester molecules, lead to a

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Limiting the molecular weight of the resulting polyesters. In contrast, when using modifiers, which attach themselves to the interior of the molecular chain do not impose such a limitation. Sometimes it is cheap if both types of modifiers are attached to the polyester molecules. But there are both types of modifiers become part of the polyester molecules, a permanent modification occurs, which can be achieved by washing or dry cleaning and the like can no longer be removed.

In the production of the modified terephthalic acid polyester for use as materials for the fibers according to the In the present invention, a compound (hereinafter referred to as "dye-modifying compound") can be incorporated into the polyester which is the desired piperidine group and (if applicable) contains the desired bond, incorporate by known methods such as those described in U.S. Patent 3,624,181 are. These methods include (1) a conventional copolymerization method in which the dye-modifying Compound is incorporated by transesterification or by direct esterification, and (2) a melt blending process in which the dye-modifying compound to the polyester molecule is bound, so that very similar structures are obtained as in the copolymerization process. If this is the For the purpose of increasing the melt viscosity of the modified polyester, it is desirable to use small amounts of chain branching compounds, such as trimesic acid, trimethylolethane or pentaerythritol, use. If necessary, you can also Add polymerization accelerators such as diphenyl terephthalate. Salts of the dye-modifying agents can also be used Compounds that are produced with acids of phosphorus (e.g. phosphoric acid, diphenylphosphinic acid, phenylphosphinic acid), for the production of the modified terephthalic acid

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use polyester.

As already mentioned, the tetramethylpiperidine group is attached to the polyester molecule directly or via an oxyalkylene group, an alkylene group / an aromatic amide group or an amino-s-triazine group.

For the production of the modified terephthalic acid polyester according to that embodiment of the invention in which the 2,2,6,6-tetramethylpiperidine group is attached directly to the polyester molecule, suitable dye-modifying agents Compounds are: 2,2,6,6-tetramethyl-4-hydroxypiperidine, 1-low Alkyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, where the lower alkyl group of a hydrocarbon having no more than 18 carbon atoms, preferably 1 to 4 carbon atoms, is derived, namely preferably 1,2,2,6,6-pentamethyl-4-hydrojcypiperidine, also l-methoxymethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and 1,1'-ethylene-bis (2,2,6,6-tetramethyl-4-hydroxypiperidine).

According to a preferred embodiment of the invention the fibers are made from modified terephthalic acid polyesters in which 2,2,6,6-tetramethylpiperidine groups have a Kind or more kinds bound to the polyester molecule chain in positions No. 1 and / or No. 4 via oxyalkylene groups are. These oxyalkylene linkages include - (0A) - or - (0A) -0-, where η has a value from 2 to about 80 and A Means ethylene, propylene, or both. For the sake of simplicity, these are particular dye modifying compounds referred to here as piperidine alcohols. The substituents in position No. 1 or No. 4 may also be other than that such as HO, a monovalent hydrocarbon group, or the compounds can simply be unsubstituted

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be. When the number of oxyalkylene linking groups is relatively low is (e.g. 3 or less), the polyester is relatively hydrophobic, and in weakly acidic Dye liquors, such as those with pH values of 4.5 and more, then generally do not reach their full potential achieved at dye receptive sites. But if the The average number of oxyethylene groups is greater than ten, the polyesters are significantly more hydrophilic, and this leads to a more complete utilization of the highly basic, dye-receptive sites and the ability to to be colored from weakly acidic dye liquors.

Those dye-modifying compounds that are im In the context of the invention, oxyalkylene substituents may have be prepared by condensing an alkylene oxide with one or more of the following compounds: 2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl 1-4-hydroxypiperidine, 1-low Alkyl ^^^ iG-tetramethyl ^ -hydroxypiperidine (as defined above) and 1-methoxymethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine. If the reaction is not carried out catalytically, an alkylene oxide molecule attaches itself to the secondary nitrogen atom, and then the reaction stops. This non-catalytic reaction is usually carried out at elevated levels Temperatures and pressures carried out to ensure their complete course. If the condensate is a diol, it can be used as a dye-modifying compound without further condensation. Preferably, however, the product especially if it is a monohydric alcohol, condensed with further alkylene oxide. If this Product or any other suitable monohydric alcohol is condensed with further alkylene oxide, the condensation becomes carried out in the presence of a catalyst. Suitable cata-

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Analyzers are, for example, sodium hydride, potassium hydride and lithium aluminum hydride . If appropriate, it is also possible to use mixed alkylene oxides or the condensation initially with an alkylene oxide carry out until a given amount of alkylene oxide units has accumulated and then with another alkylene oxide. The catalytic addition of an alkylene oxide to a compound with a reactive hydrogen atom is known to lead not to a specific compound, but to a mixture of compounds with different numbers of oxyalkylene units, and therefore such mixtures are characterized with reference to the average number of oxyalkylene units. Primary alcohols are known to condense with alkylene oxide faster than secondary alcohols, and if so Both types of alcohol are present, the distribution in the product composition is influenced by them. Because the nitrogen atom can be alkylated, it can first be reacted with a halogenated alcohol (e.g. 2-chloroethanol), and optionally this product can then be condensed with an alkylene oxide.

The alkylene oxide condensates are of higher molecular weight significantly less volatile than those of lower molecular weight and are therefore suitable for use in polyester forming Reaction mixtures preferred because fewer precautionary measures are required to prevent they escape than with low-boiling compounds. Furthermore, the use of ethylene oxide condensates leads to higher molecular weight for better dyeability of the fibers. According to the invention, the mean number is therefore Oxyalkylene units at least 3 and usually 5 to 80. However, the number of oxyalkylene units should be preferred between 10 and 40, in particular between 20 and 30.

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Also suitable for the purposes of the invention are dye-modifying agents Compounds compounds of 2,2,6,6-tetramethylpiperidines, which have substituents in position no. 1 and / or in position no. 4 of the piperidine ring, which subsequently form alkylene bonds with the polyester molecules. These dye-modifying compounds include 1- (2-Hydroxyäthy1} -2,2,6,6-tetramethy! Piperidine, 1- (2-hydroxyethyl) -2,2,6,6-tetramethy1-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4- (2-hydroxyethyI) piperidine, 1,2,2,6,6-pentamethyl-4- (2-hydroxyethyl) piperidine, the ethyl ester of 2,2,6,6-tetramethyl 1-4-piperidine acetic acid and the diethyl ester of 2,9-bis (2,2, -6,6-tetramethyl-4-piperidyl} decanedioic acid. The first two of these dye-modifying compounds can be obtained from the corresponding 2,2,6,6-tetramethylpiperidine compounds conventional ethoxylation reactions and / or by reaction with chloroethanol. The making of the last four of the compounds given above occur only after known reactions, but require multi-stage syntheses.

Dye-modifying compounds which can also be used for the purposes of the invention and lead to the formation of an aromatic aromatic binding group between the 2,2,6,6-tetramethylpiperidine group and the polyester molecules are 5 - / (2,2,6,6-tetramethyl 1-4-piperidinyl ) sulfamyl_7 ^{iso Pntnals} acid dimethyl ester, 5- / 7l, 2,2, 6, 6-pentamethyl 1-4-piperidinyl) sulfamoy 1 / - isophthalic acid dimethyl ester, 5- / 72,2,6,6-tetramethyl-4-piperidinyl ) sulfamoyl / isophthalic acid diethyl ester, / (2,2,6,6-tetramethyl-4-piperidinyl) sulfamoyl- ^fluorene- 9,9 -dipropionic acid dimethyl ester, / 72,2,6,6-tetramethyl-4-piperidinyl) sulfamoyl? - fluorene- 9,9 -dipropionic acid, 5- / 7l, 2,2,6,6-pentamethyl-4-piperidinyl) sulfamoyl7isophthalic acid, 5- / 72,2,6,6-tetramethyl-4-piperidinyl) sulfamoyl7isophthalic acid, N- (2 , 2,6,6-tetramethyl-

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4-piperidinyl) terephthalamic acid methyl ester and m- / (1, 2,2, 6,6-pentamethyl-4-piperidinyl) sulfamoyl-7benzoic acid methyl ester. Of those dye-modifying compounds that exist between the polyester molecular chains and the 2,2,6,6-tetramethylpiperidine groups make aromatic amide bonds, those who make sulfonamide bonds are opposed to those who which produce carbonamide bonds are preferred.

The other group of dye-modifying compounds useful for the purposes of the invention create an amino-s-triazine linkage between the 2,2,6,6-tetramethylpiperidine group and the polyester molecules. This group of dye-modifying compounds includes 2,4-dimethoxy-6- / 72,2,6,6-tetramethyl-4-piperidinyl) amino / -s-triazine, 2,4-dimethoxy-6- / l _r 2,2 , 6,6-pentamethyl-4-piperidinyl) amino7-s-triazine, 2,2'- / 4,6-h ± s-li2,2,6,6 -tetramethyl1-4-piperidinyl) arainoy-s-triazine -2-ylimino7diethanol and the corresponding pentamethyl derivative, N, N ^I - / 6- / l2,2,6,6-tetramethyl-4-piperidinyl) amino7-s-triazine-2,4-diyl / diglycine and the corresponding pentamethyl derivative, 2-methoxy-4,6-bis (2,2,6,6-tetramethyl-4-piperidinylamino) -striazine and the corresponding pentamethyl derivative as well as 2,2 '- / 6- (2,2,6,6-tetramethyl) 4-piperidinylamino) -s-triazine-2,4-diyldiimino / diethanol.

In detail, the "Manufacture" is some of the above mentioned dye-modifying compounds and their incorporation in Terephthalic acid polyester for the purpose of making practical and preferred fibers which can be dyed with acid dyes according to FIG Invention illustrated in the examples below.

The dye-modifying compounds described above generally have good heat resistance. These compounds can usually be used at elevated temperatures.

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as required in the manufacture and melt spinning of the modified polyester. at
the dye-modifying processes suffer from these processes
Compounds do not degrade so strongly that they become colored
Form by-products. They also generally do not generate
so much decomposition products that they could have an adverse effect on the polyester, such as an excessive decrease in the molecular weight of the polyester.

The thermal stability of the dye-modifying compounds can be tested by simple laboratory procedures. So
the connection to be investigated can be put into a glass tube, for example
bring in, which is then flushed thoroughly with inert gas, to a pressure of less than 1 torr (1 mm of mercury
absolute pressure) evacuated and finally melts down. That
The fused tube is then heated for at least as long and at a temperature that is at least as high as the connection in question in the production of threads from the modified one
Polyester would be subjected to heat treatment. In
typically compound 10 to 180, for example, is heated
Min. To 283 ^° C. If the dye-modifying compounds suitable for the purposes of the invention are examined after such a heating test, it is found that they have practically not changed on heating.

The extent to which the dye modifying compound degrades or discolors the linear terephthalic acid polyester can
can be determined by conventional methods, such as the method described by RS Hunter in "Journal of the Optical Society of America", Volume 50, January 1960.
With this method, reflectometer measurements are carried out on spun fibers and converted into values for the degree of whiteness.

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converts that indicate the extent of degradation or discoloration.

To the linear terephthalic acid polyesters within the scope of the invention include polyesters made from terephthalic acid or from ester-forming derivatives thereof. If nothing to the contrary is indicated, copolyesters (i.e. polyesters made of 3 or more Reaction participants who each have two ester-forming groups) understood. Optionally, the polyesters Additives (e.g. matting agents, agents to increase viscosity, optical brighteners, oxidation retardants and the like) contain. Furthermore, the threads made from these polyesters can have a wide variety of cross-sectional shapes, e.g. round, multi-leaf or hollow.

Examples of linear, fiber-forming terephthalic acid polyesters are polyethylene terephthalate, polytrimethylene terephthalate, Polytetramethylene terephthalate, polyethylene terephthalate / isophthalate (85/15), polyethylene terephthalate / hexahydroterephthalate (90/10), poly (hexahydro-p-xylylene) terephthalate and terephthalic acid copolyester, which contain aliphatic dicarboxylic acid units (especially terephthalate / adipate and terephthalate / dimerate copolyester).

The invention is particularly valuable by working with acid dyes Dyeable fibers made from modified copolyesters are made available which contain at least 85 mol% ethylene terephthalate units contain. Such copolyesters are therefore preferred for the purposes of the invention. Modified ones are particularly preferred Copolyester of ethylene terephthalate / adipate with 3 to% by weight adipate units. Modified copolyesters of the latter,

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particularly preferred types generally have a relatively high affinity for acid dyes even when subjected to heat-setting treatments after stretching have been.

The modified linear terephthalic acid polyesters suitable for the purposes of the invention can have relative viscosities from 7.5 to 85, but for most textile uses preferably have relative viscosities between 11 and 30. The relative viscosity is here as the ratio of the viscosity of a 4.75 % by weight polyester solution in hexafluoroisopropanol, which contains 100 parts by volume of concentrated sulfuric acid per million parts by volume, to the viscosity of the solvent consisting only of hexafluoroisopropanol and sulfuric acid
it's correct.

defined by means. Both viscosities are loaded at 25 ° C

The nitrogen content of the modified polyester can be determined by any of a number of conventional methods, such as micro-Kjeldahl analysis. The Sfcxckstoffgehalte given here refer only to the nitrogen atoms in the dye-receptive site (ie, in the 2,2,6,6-Tetramethylpiperidinring), but not to other nitrogen atoms, which may be included in binding groups (for example, the other nitrogen atoms in the aromatic amide bonds or the amino-e-triazine bonds).

The fibers made from the linear terephthalic acid polyesters modified according to the invention can be dyed well under relatively weak acidic conditions. This good colorability is influenced not only by the base strength of the nitrogen contained in the 2,2,6,6-tetramethylpiperidine group, but also by other factors. It was found,

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that the dyeability generally improves with increasing amounts of conventional copolyester units (eg adipate units) in the modified linear terephthalic acid polyester molecules. In the case of polyesters in which the 2,2,6,6-tetramethylpiperidine groups are bonded to the polyester molecules via oxyalkylene radicals, the colorability usually improves as the number of oxyalkylene units in the bond increases. Dyeability is also improved by increasing the concentration of the nitrogen-containing dye receptive sites in the modified polyester. Optionally, one can increase the dyeability of a higher temperature and by using more acidic dye liquors and / or dye liquors. Suitable dyes for the fibers according to the invention are, for example, CI Acid Blue 25 (CI. 62055), CI Acid Red 4 (CI. 14710), CI. Acid Yellow 40 (CI. 18950) and CI. Acid Green 25 (CI. 61570). The CI. Numbers of these dyes are those of the "Color Index", 2nd edition, 1956. When the fibers according to the invention are dyed with such acid dyes, they show good resistance to fading in sunlight.

There are several conventional methods of determining the quality of the coloration Methods. For example, you can easily determine the amount of dye taken up by the fibers from the dye flatten determine by measuring the concentration of the dye in the dye liquor before and after dyeing the fibers; one can also measure the depth of hue (or darkness of the color) achieved on the colored sample. Individual fibers can be examined in their cross-section under a microscope to determine whether the fiber is through has been colored through its entire cross-section or only near its surface (ie "ring-colored").

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Examples

The following examples illustrate typical and presently preferred methods for practicing the invention specified. Unless otherwise indicated, the following general procedures are used. Details regarding the conditions used and the characteristic properties of the products are given in Tables I to IV summarized.

(1) A dye-modifying compound is prepared. ·

(2) A modified linear terephthalic acid polyester

is made by one of two general methods described below.

The modified polyester is prepared by a process referred to hereinafter as melt blending. The dye-modifying one Connection and the dry linear terephthalic acid polyester are in one with stirrer and connections Introduced a vessel equipped for introducing and withdrawing gas. The vessel is flushed out with inert gas. The contents of the vessel are stirred until they melt and the reaction between the dye-modifying compound begins and heated the polyester. Then the reaction is continued under vacuum with continued stirring and heating, whereby the ethylene glycol is withdrawn and the modified ester is formed. Then inert gas is passed through again into the vessel and cools the modified polyester. The polyester is then placed in a rotating cutter cut into particles called "flakes"

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and pass through a perforated metal screen with holes 0.318 cm in diameter. If necessary, the modified Polyester is further polymerized by heating the flakes in vacuo to elevated temperatures.

According to the second general method, the modified polyester is made by copolymerizing the dye-modifying Compound produced in a polyester-forming starting mixture. The dye-modifying compound is added to the monomeric starting material or to the prepolymer, depending on which method is most appropriate for carrying out the procedure.

(3) The modified polyester is spun from the melt and using conventional methods in a laboratory facility or drawn out into textile thread in a large-scale plant.

(4) A sample of the yarn, a strand or one made from the yarn Tissues are typically dyed as follows:

The sample is placed in an aqueous washing bath containing a wetting agent in a concentration of 1%, based on the Weight of the sample (hereinafter abbreviated as "owf"), and tetrasodium pyrophosphate contains at a concentration of 1% owf. The bath boils at a rate of 1.7 ° C / min heated. After the sample has remained in the boiling bath for 30 minutes, it is removed from it and washed with hot water flushed.

The washed sample is then placed in an aqueous dye liquor. The dye liquor has a temperature of about 38 C, contains 1% owf wetting agent and has a with the help of phosphoric acid or tetrasodium pyrophosphate to the desired level

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set pH value. The sample is stirred in the bath for 5 minutes, after which 2% owf CI Acid Blue 25 (CI 62055) and optionally 15% owf of a carrier are added to the dye liquor. Then, the dye liquor is at a rate of 1.7 ° C / min to either the atmospheric boiling point or, if the dye bath is in a Druckfärbevorrichtung, heated to 121 ⁰ C. The sample is kept in the dye liquor for 90 minutes.

Then, the dyed sample is taken out from the dye bath and inserted into a second aqueous wash bath having a temperature of 38 ⁰ C and containing 1% owf wetting agent, and O, 5% glacial acetic acid. The temperature of this washing bath is raised at a rate of 1.7 ° C / min to 82 ⁰ C and held for 30 min. At this level. The sample is then washed thoroughly with cold water and dried. .

The washing baths and dye liquors described here generally have a weight ratio of bath to sample of about 40: 1 up. A condensation product is usually used as the wetting agent of octylphenol with 9 to 10 moles of ethylene oxide. The carrier to be added if necessary is usually too about 50% from p-toluic acid methyl ester, 25% from benzoic acid methyl ester and 25% biphenyl (all data are based on weight).

In all of the examples below, the modified polyester fibers show only insignificant signs of discoloration or Degradation due to the dye-receptive sites in the polyester molecules, and all fiber samples can then be dyed satisfactorily.

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Example 1/3

In this example, pasers are made from a modified linear Terephthalic acid polyester, called 2,2,6,6-tetramethylpiperidine groups directly attached to the end of the polyester molecule, made and colored. As a dye-modifying agent Compound for Samples I-a and I-b is commercially available 2,2,6,6-tetramethyl-4-hydroxypiperidine (hereinafter referred to as "THP") is used, while for sample I-c the dye-modifying compound is 1,2,2,6,6-pentamethyl-4-hydroxypiperidine (hereinafter referred to as "PHP") is used.

The PHP is made like this: A mixture of 18 g THP, 18 g aqueous formaldehyde solution (37 percent by weight CHpO) and 4 ml of formic acid (with a water content of 1 percent by weight) is in a 100 ml round-bottomed flask for 7 hours heated in the steam bath. The contents are cooled with caustic soda made alkaline and extracted with ether. The ether extract is dried over anhydrous magnesium sulfate and the Ether evaporated. The residue, a white solid, is sublimated at 90 ° G under absolute pressure purified from 0.05 mm Hg. The purified PHP has a melting point of 70-71 ° C.

Sample I-a

A mixture of 1.2 kg of polyethylene terephthalate (hereinafter referred to as ^M 2GT ") with a relative viscosity of 46.9 and 19» 2 g THP is introduced into a 3 liter round bottom flask for mixing in the melt Inlet and outlet connections and a stirrer are purged with nitrogen and evacuated to an absolute pressure of 1 mm Hg or less. While the contents of the flask are under vacuum, the flask is sealed and kept at 285 ° C. with stirring Heat the salt bath until the contents melt, then heat an additional 15 minutes at 285 ° C. The flask is turned

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removed from the salt bath and the contents stirred for a further 5 minutes and then left to cool under nitrogen at a pressure of 1 atm. At this point the modified polyester has a relative viscosity of 10.7. The polyester is then polymerized further in the solid phase and spun from the melt into threads, which are wound up as yarn to form a package at a speed of 64 m / min. The yarn is drawn in a two-stage process, in that it is drawn off the package, fed to a feed roller at a speed of 3.36 m / min, in a first stage on a stretching rod at 100 ° C. at a speed of 15.1 m / min stretched, further stretched in a second stage at a speed of 15.5 m / min and finally wound onto another yarn package. The conditions under which the process steps described above are carried out and the properties of the modified polyester threads thus obtained are shown in Table I. The yarn is then processed into a knitted fabric. The knitted fabric is dyed according to the general process described above in a printing dyeing machine, with the difference that the dye liquor has a temperature of 138 ° C and contains 4 # owf dye and 40 fo owf 2-chloro-4-phenylphenol as a carrier, while the second wash bath contains 2 g sodium carbonate per liter of water (instead of glacial acetic acid). The pH of the dye liquor is adjusted to 3.5. The fabric sample can be satisfactorily dyed in a deep blue tone.

Sample I-b

In this sample, as for sample I-a, THP is used as the dye-modifying compound to make the threads of a modified linear terephthalic acid copolyester.

A mixture of 1.3 kg of a linear terephthalic acid copolyester and 11.5 g of THP is as described for sample I-a was mixed in the melt. The copolyester has a relative viscosity of 39.8 and contains 93.4 weight

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percent ethylene terephthalate units and 6.6 percent by weight ethylene adipate units. Polyethylene terephthalate / adipate copolyesters are hereinafter referred to as "2GT / 6". The melt-mixed, modified polyester, which has a relative viscosity of 12.2, is cut into flakes, polymerized in the solid phase and spun into a 34-ply yarn, which at a speed of 274 m / min into a package is wound up. The yarn is withdrawn from the yarn package at a speed of 76 m / min via feed rollers via two pins, of which the first has a temperature of HO and the second has a temperature of 158 ° G, to a forging roller, which rotates at a peripheral speed of 250 m / min. The drawn yarn then runs around another roller assembly rotating at 248 m / min and is wound up at a speed of 244 m / min. The yarn is processed into a knitted fabric. Samples of the knitted fabric are dyed in a print dyeing device according to the general procedure described above at pH values of 3.0, 5.0 and 6.0, respectively, but with the paraffin concentration in the parquet liquor 4 $> owf and the carrier concentration 40 $ owf is. The samples can be colored satisfactorily in a deeper blue shade than sample Ia, although the concentration of nitrogen-containing, dye-receptive sites in the polymer molecule of example Ib is lower than that of example Ia (0.06 fi compared to 0.11 $). This result is attributable to the use of a modified copolyester (2GT / 6) for the sample Ib instead of a modified homopolyester (2GT) for the sample Ia.

Sample I-c

A modified copolyester with PHP groups attached to the ends of the polyester molecules is made, by adding PHP in a continuous mixer at a concentration of 0.612 percent by weight of the polyester melt mixes. The polyester is the same polyethylene

- 21 409813/1097

$ Z

terephthalate / adipate copolyester (2GT / 6), the avch for the sample I-b was used. The melted substances are the Mixer fed by metering pumps and mixed until the piperidine compound is practically completely transesterified reacts with the polyester. The melted reaction product flows out of the mixer continuously. The mixer temperature is 285 C and the residence time in the Mixer 5.25 minutes. The still melted polyester is then spun into a 34-thread yarn and immediately one The drawing zone is fed in, where the yarn is drawn in two stages. The yarn travels from a feed roll at one speed of 503 m / min to a steam stretching nozzle and then to forging rolls operating at a surface speed at a speed of 2285 m / min. The nozzle is filled with water

water steam of 3.52 kg / cm, and the temperature in the stretching nozzle is 225 ° C. The drawn yarn then runs to a second drawing zone and a second unit of forging rollers at a speed of 2293 m / min. The drawn yarn is passed at a speed of 2280 m / min over heat treatment rollers which are at a temperature of 115 ° C. in order to reduce the shrinkage of the yarn. The drawn yarn is wound onto a yarn package and processed into a knitted fabric. Samples of the knitted fabric are under pressure in dye liquors containing 4 £ owf dye and 20% owf methylnaphthalene as a carrier include, dyed at pH values of 4.0, 5.0, 6.0 and 7.0, respectively. All samples can be colored well and take on deep blue shades at the lower pH values and medium blue shades even at the higher pH values.

Example 2

In this example, pasers are made from a modified linear Terephthalic acid polyester produced in which the 2,2,6,6-tetramethylpiperidine groups via oxyalkylene groups the polyester molecular chains are bound. In the first sample Ha, which is a preferred embodiment of the

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is the modifier in dtn polyester molecular chains bound to the same. In the remaining five samples, the modifier is attached as a terminal group.

Six dye-modifying agents are used to prepare the samples of this example Compounds prepared, namely (1) a condensation product of ethylene oxide and 2,2,6,6-tetramethyl-4-hydroxypiperidine, 20 oxyethylene units on average per molecule and hereinafter referred to as "THP-20E0" is, (2) a condensation product of ethylene oxide and 2,2,6,6-tetramethylpiperidine, which per molecule on average Contains oxyethylene units and hereinafter referred to as "TMP-20E0" is, (3) a condensation product of ethylene oxide and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, which per molecule generally contains 10 oxyethylene units and hereinafter referred to as "PHP-10E0" is called, (4) just like (3) »but with a average content of 20 oxyethylene units per molecule, hereinafter referred to as "PHP-20E0", (5) a condensation product from propylene oxide and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, which contains an average of 20 oxypropylene units per molecule and hereinafter referred to as "PHP-20P0", and (6) a condensation product of alkylene oxide and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, per molecule an average of 5 oxyethylene units in one block and 5 oxypropylene units in one block and hereinafter referred to as "PHP-5EO-5PO" referred to as. These dye-modifying compounds are produced as follows:

(1) "THP-20E0

A stainless steel reactor is charged with 70.5 kg of 2,2,6,6-tetramethyl-4-hydroxypiperidine and 34 kg of diethylene glycol diethyl ether. The pressure in the reactor is reduced to 0.15 atm and the reactor is pressurized with nitrogen to an overpressure of 1.05 kg / cm. The evacuation is repeated and the nitrogen overpressure is then increased to 0.21 kg / cm ²

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40981 3/1 097

set. The contents of the vessel turn green and heat to 125 ° C; A sample taken at this time, the sample contains less than 0.2 fo water. At 125 ° C, a total of 22 kg of ethylene oxide are added at such a rate that the temperature rises to 145-155 ° C. The reactor is equipped with valves in such a way that the flow of ethylene oxide stops when the overpressure exceeds 2.1 kg / cm or the temperature exceeds 150 ° C. The batch is kept at a temperature not below 125 ° C. for 8 hours while stirring. A sample taken at this point contains less than $ 1> unreacted 2,2,6,6-tetramethyl-4-hydroxypiperidine.

110 g of sodium hydride, dispersed in 110 g of mineral oil, are then added as a catalyst and the batch is stirred in for 1 hour Passing nitrogen through. The evacuation and pressurization are then repeated and 378 kg of ethylene oxide are added, as described above. The supply of ethylene oxide is interrupted and the pressure by reaction with the ethylene oxide let sink. Then one lets the batch at 115 C

P cold. The reactor pressure is set to 1.05 kg / cm,

increased with nitrogen to an overpressure of 1.4 kg / cm, like-

adjusted to 1.05 kg / cm and again with nitrogen

increased to an overpressure of 1.4 kg / cm. Nuclear magnetic resonance analysis is carried out on a sample taken at this point in time found that the product contains an average of 18 to 22 oxyethylene units »per piperidine group. The catalyst is rendered ineffective by adding 280 g of acetic acid and stirring is carried out for 1 hour.

(2) TMP-20E0

A dry 400 ml stainless steel bomb is charged with 100 g of 2,2,6,6-tetramethylpiperidine. the The bomb is cooled to -78 ° G, evacuated and filled with nitrogen and evacuated again. Then the bomb is placed on a weighing pan and attached through a flexible hose a source of ethylene oxide attached. Man directs ethylene

- 24 40981.3 / 1097

oxide into the bomb until it has added 40 g. then the bomb is sealed, the connection with the ethylene source interrupted and the bomb 1 hour at 100 ° C, 1 hour at 110 ° C, 1 hour at 120 ° C and 8 hours Heated 155-160 ° C. A bomb becomes a solid white one Discharged product weighing 131 g. This procedure is repeated with half of the above amounts. The products both approaches are combined with one another. To remove impurities, the product is dissolved in ether, activated charcoal is added to the solution and the suspension for 5 minutes heated to boiling. Then the solution is filtered and cooled. From the filtered, cooled solution, one obtains white crystals of 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidine, which melt at 93-94 ° C. One with thermometer, mechanical stirrer, gas inlet tube and one vertical standing cooler with a bubble counter connected to its outlet 1st equipped 5 liter flask is charged with 135 g of this purified product. The device will weighed, purged with nitrogen and the product stirred and melted at 100 ° C. If the batch is homogeneous while stirring a dispersion of 0.175 g of sodium hydride in 0.175 g of mineral oil is added. Then you go to the Liquid with stirring gaseous ethylene oxide at such a rate that no gas through the bubble counter escapes, with the flat ended additive, the piston will again with it Purged with nitrogen, cooled and weighed. Here it is determined that 618 g of ethylene oxide have been absorbed. The catalyst is by adding 0.44 g of acetic acid and 10 Stirring for minutes destroyed. It is calculated that the product has an average of 20.3 oxyethylene units per piperidine group contains, and a neutralization equivalent of 1002 is determined for the product.

(3) PHP-1OE0

In one with thermometer and nitrogen inlet capillary equipped. 5 liter flask is a batch of 766 g

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BP-933 2346J3A

1,2,2,6,6-Peiitamethyl-4-hydroxypiperid: \ o (cf. Example 1, sample Ic, for the production of PHP) purified. The temperature is increased to 90 ° C and the pressure is decreased to 1-2 torr and these conditions are maintained for 30 minutes to drive off water and volatile acidic components such as carbon dioxide. The residue weighs 742 g (4.32 mol). The flask is then fitted with a mechanical stirrer, a gas inlet tube (instead of the inlet capillary) and a vertical cooler with a bubble counter connected to its outlet. The device is flushed with nitrogen for 10 minutes and the residue is melted again by heating to 80 ° G with stirring, whereupon a dispersion of 1.08 g of sodium hydride in 1.08 g of mineral oil is added. Gaseous ethylene oxide is introduced into the melt with stirring at such a rate that no gas escapes through the bubble counter. The weight loss of the cylinder from which the ethylene oxide is taken serves as a rough measure of the amount of ethylene oxide absorbed. The molecular composition of the compound thus obtained is calculated based on the weight of the flask and its contents before and after the addition of the ethylene oxide. When the addition is complete, the flask is flushed with nitrogen and cooled to below 50 ° C. The condenser is removed and the flask weighed again. The weight increase is 1914 g _f, which corresponds to a product with a calculated average content of 10.1 oxyethylene units per piperidine group. 2.7 g of acetic acid are then added and the mixture is stirred for 10 minutes in order to render the catalyst inactive. The product has a neutralization equivalent of 623.

(4) PHP-2O-E0

The process described for making PHP-10E0 is also used to make these dye-modifying ones Compound used except that double the amount of ethylene oxide is added.

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(5) PHP-20P0

One with a stirrer, side arm attachment, thermometer, and a pressure reliever Dropping funnel and a Dewar cooler, at its An oil-filled bubble counter is connected to the outlet, the flask is provided with 87 g of purified 1,2,2,6,6-pentamethyl-4-hydroxypiperidine .shipped. The condenser is cooled with a mixture of solid carbon dioxide and acetone. Of the Flask is purged with nitrogen and charged with a dispersion of 0.125 g sodium hydride in 0.125 g mineral oil. Then the flask is heated to 150-170 ° C, whereupon 1,2-propylene oxide is discharged from the dropping funnel at such a rate adds that only a weak reflux forms in the condenser. As soon as the addition of the Propylene oxide no further reflux can be determined, the batch is passed through with nitrogen chilled. A comparison of the weight of the flask with its contents before and after the addition of propylene oxide shows that 580 g of propylene oxide have been included, which corresponds to an average content of 19> 7 oxypropylene units per piperidine ring. The catalyst is destroyed by adding 0.25 g of acetic acid and stirring for 10 minutes. The product has a neutralization equivalent of 1333.

(6) PHP-5EO-5PO

Initially the procedure is carried out using the same method and apparatus as described above for the manufacture of PHP-10E0 has been described with the Difference that (1) the catalyst is only destroyed after the final compound has been made and that (2) the following amounts are used: 172 g (1 mole) 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, 0.25 g sodium hydride in 0.25 g of mineral oil and 213.5 g of ethylene oxide. this leads to the formation of an intermediate product with a middle Content of 4.9 oxyethylene units per piperidine ring (PHP-5E0). The flask with this intermediate product is then equipped in such a way that that it corresponds to the device according to the above

- 27 40981 3/1097

Description of the manufacture of PHP-2OPG verv. ^r 3nd3t has been. The apparatus is operated in the same way, and 285 g of propylene oxide are added, which leads to a calculated average content of 4.9 oxypropylene units per piperidine ring, these units being bonded to the oxyethylene units as blocks. Finally, the catalyst is destroyed by adding 0.62 g of acetic acid. The end product has a neutralization equivalent of 656.

Sample II-a

This sample corresponds to the preferred embodiment of the invention.

A three-necked round-bottomed flask is fitted with a stirrer, distillation attachment and nitrogen inlet tube. The flask is charged with 450 g of dimethyl terephthalate, 285 ml of ethylene glycol and, as a catalyst, 0.20 g of Mn (C ₂ H ₅ O ₂ ) ₂ · 4 H ₂ O and 0.14 g of Sb ₂ O ₅ in solution in 23 ml of ethylene glycol . The flask is gradually heated in a Wood's metal bath until 198 ml of methanol has distilled off. A solution of 1.55 g of H ₅ PO is then used. (100 percent) in 15.9 ml of ethylene glycol, 23.0 g of adipic acid and 30.4 g of ΪΗΡ-20Ε0. The mixture is heated to 225-259 ° C at atmospheric pressure for 48 minutes. Then the pressure is gradually reduced to 0.3 torr over one hour and 27 minutes. The polymerization is continued at 0.3 torr or lower pressure for 2 hours and 5 minutes. The flask is then pressurized with nitrogen, removed from the bath and cooled under nitrogen. The relative viscosity of this material is 7.3. The product is ground to a particle size of less than 2 mm and crystallized by heating under nitrogen at 130-200 ° C. for 3 hours, followed by polymerization in the solid phase at 0.2 torr and 200 ° C. over 16 hours
the relative viscosity to 17.7.

200 ° C carried out in the course of 16 hours. It increases

- 28 - 0.9 8 1 3/1097

This material is spun at a block temperature of 249 ° C. and a winding speed of 108.8 m / min to form a 14-ply yarn. The yarn has a relative viscosity of 14t4 and contains 0.057 percent by weight nitrogen and 4.56 percent by weight adipate units. The yarn is drawn 5.6 times at a temperature of the feed rollers of 68 ° C. and a temperature of the drawing rollers of 90 ° C. and then relaxed at 180 ° C. for 5 minutes. If the relaxed yarn is dyed for 90 minutes at 100 ° C. and a pH of 4.5 with 3 fo owf Acid Blue 40 (CI. 62125) without a carrier, it takes on a medium shade. When using as the carrier 10 io owf diphenyl, the yarn assumes upon dyeing under the same conditions to a dark tone. A dark blue tint is also obtained by dyeing under pressure under the same conditions.

Sample II-b

This sample represents another preferred embodiment of the Invention.

The monomer is prepared by adding 5 kg of dimethyl terephthalate, 3.35 kg of ethylene glycol and 120 ml of a solution of 2, 45 g Mn (C ₂ H ^ O ₂ ) to a stainless steel still, which has a drain valve at the bottom. ₂ · 4H ₂ O and 1.69 g of SbpO ^ in ethylene glycol are charged

Heated to 240 ° C. over the course of 3 hours, 1650 g of methyl alcohol and then 750 g of ethylene glycol being distilled off in succession. The monomer obtained in this way is withdrawn into a stainless steel autoclave which is equipped with a stirrer, inlet opening, vacuum distillation system and extrusion valve. The autoclave is filled with 285 g of a glycol solution of adipic acid dihydroxyethyl ester (corresponding to 163.6 g of adipic acid), 24 ml of a solution of 1.79 g of 100 percent phosphoric acid (EUPO.) In ethylene glycol and 27 ml of a 20 percent slurry of TiO ₂ in Ethylene glycol charged. The pressure decreases slowly over the course of 2.5 hours

- 29 - 4098 13/1097

reduced to 5 torr. Then the autoclave is filled with inert gas pressurized and charged with a solution of 317 g of PHP-20E0 in 200 ml of ethylene glycol. The pressure will be gradual. reduced to 1.3 Torr over the course of 30 minutes and the Polymerization continued at 275 ° C for 2 hours. Then the melt is extruded, cooled and cut into flakes, which have a relative viscosity of 11.1.

Five similar batches are mixed together and then polymerized further in the solid phase. This increases the relative viscosity of the polyester flakes to 21.2.

The polyester is spun into a 10-ply yarn that at a speed of 640 m / min into a package is wound up. 57 such yarn packages are combined into a strand by winding. The strand is made by a number of feed rollers at a speed of 12 m / min through an aqueous bath containing a lubricant and has a temperature of 50 ° C, fed to a series of forging rollers, which rotate at 43 m / min and in one An aqueous bath containing lubricant is heated to 70 ° C, whereupon the strand forms an aggregate of four 140 ° C working rollers to heat treat it at a constant length. Then the strand is crimped into a gland crimp device crinkled and relaxed in a hot air oven at 180 ° C for 5 minutes. The stretched, relaxed ones Threads have a denier of 13.0 denier.

Similarly, a 50-filamentous yarn is spun, drawn, crimped, relaxed at 150 C and, a strength of 3.7 g / d, an ultimate elongation of 35 $> and a relative to staple fibers having a linear density of 2.8 Cut viscosity of 19.4.

Samples of both products are produced by the dyeing process described above at atmospheric pressure and 100 0 dark blue.

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409813/1097

5
colors, although Acid Blue 40 (CI. 62125) is used as the dye.

Sample II-c

Polyester threads that can be dyed with acid dyes are made from a modified polyethylene terephthalate / adipate gopolyester (2GT / 6) made of 5.5 weight percent adipate units contains, the modifier used being TMP-20E0. The modified polyester is produced by mixing in the melt and subsequent polymerisation in the solid phase «.

Mixing in the melt is done by placing a test tube loaded with 75 g 2GT / 6 polyester flakes and 4.6 g TMP-20E0. The glass is alternately evacuated and with five times Purged with nitrogen, whereupon the contents are melted by heating to 265-270 ° C. under nitrogen. Under these conditions the mixture is stirred for 0.25 hours. The pressure is then reduced to less than 1.5 torr and stirring is continued Continued for 1 hour. Then nitrogen is again introduced into the test tube. The polyester is cooled, to flake cut up and then polymerized in the solid phase at 190 ° 0 for 120 hours. The finished polyester is made from the melt too spun using a 5-ply yarn.

The yarn is drawn 4.0 times in two stages. The yarn runs from a feed roller rotating at 19.8 m / min at a speed of 46 m / min over a pen heated to 83 ° C, then at a speed of 80 m / min over a plate heated to 98 ° C. and is then wound up at a speed of 78.6 m / min.

The yarn is wound up into strands which are placed under positive pressure at a pH of 3.0 in a dye liquor that is 15 # owf Contains carrier to be colored. A satisfactory dark blue color is obtained.

- 31 -. Λ09813 / 1097

Sample II-d

Polyester fibers which can be dyed with acid dyes are made from polyethylene terephthalate (2GT), which is modified with PHP-10E0, is manufactured using a melt blending process.

The dye-modifying compound PHP-10E0 is based on 110 ° C heated and in a continuous mixer in such quantities in molten polyethylene terephthalate (2GT) injected so that a concentration of 2.57% by weight PHP-10E0 is obtained in the polyester. The mixing temperature is 288 ° C and the residence time in the mixer is 7.14 minutes. This polyester is then at a block temperature of 283 ° C and a spinneret temperature of 274 ° O to one 34-ply yarn spun. The spun yarn runs directly to a drawing zone, where it is drawn in two stages. That Yarn runs from the feed roller rotating at 377 m / min to a steam drawing nozzle and then to forging rollers, which circulate at 1646 m / min. The steam used to draw the yarn is the nozzle under an overpressure of 3.52 kg / cm, and the temperature in the drawing die is 225 ° O. The drawn yarn becomes a second drawing zone and a second aggregate of Forging rolls passed, which rotate at 1690 m / min. The second set of leak rollers is heated to 150 ° C. Then runs the yarn over relaxation rollers that rotate at 1668 m / min, and is wound up at a speed of 1657 m / min. The yarn obtained in this way is processed into a knitted fabric.

Samples of the knitted fabric are dyed under pressure at pH values of 3.0 and 5.0, respectively. The dye liquor contains $ 4> owf dye and 50 5 & owf of a vehicle consisting of 20 $ owf of the usual carrier (see. The above general description of the dyeing process) and 30 fo owf benzoic acid is acting as co-sponsor. The knitted fabrics can be dyed satisfactorily in dark blue shades.

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40.98-13 / 1097 -

DP-933
Sample II-e

Polyester threads that can be dyed with acid dyes are made from one Copolyester 2GT / 6 produced by blending in the Melt is modified with PHP-20P0. The copolyester contains 5.5 percent by weight of adipate units.

The same conditions of melt mixing, solid phase polymerization and desiccant are used Melt spinning, as used for the production of the modified polyester threads of sample II-c, with the difference that PHP-20P0 is used as the dye-modifying compound instead of the TMP-20E0. The threads are in freshly spun into a yarn. To draw the yarn in two stages, one with 19 »8 m / min rotating feed roller with 46 m / min over one to 83 ° C heated pen, passed at 90 m / min over a plate heated to 98 ° C and wound up at 88 m / min. That Yarn is made into a Gewix * k, and samples of the knitted fabric are at a pH of 3 * 0 below that for the sample II-c described conditions colored. The samples can be colored satisfactorily in a dark blue shade.

Sample II-f

Polyester threads that can be dyed with acid dyes are made from a 2GT / 6 copolyester that has been modified with PHP-5EO-5PO is. The copolyester contains 5.5 percent by weight of adipate units.

The same procedures are used as described for the production and drawing of the yarn of sample II-c. with the difference that 3.16 g of PHP-5EO-5PO are used as the dye-modifying compound and that the spinneret temperature 262 C. This yarn is then drawn up into strands and samples of the strands are kept at pH levels colored by 3.0 and 4.5, respectively. Separate samples are in a parb liquor at atmospheric pressure and in a pressure dye

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device (for overpressure) according to the examples at the beginning indicated general procedures colored.

The samples can be stained satisfactorily. In each case, a dark blue color is achieved, but this is the case with Dyeing is a little deeper under pressure.

Example 3

Threads are made from a modified linear terephthalic acid epoly ester in which 2,2,6,6-tetramethylpiperidine groups are bonded to the polyester molecular chains via alkylene groups. For the first sample, the bifunctional compound 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine (hereinafter referred to as "THP-1EO IF), the binding groups inside the polyester ^{chain, is used as the dye-modifying compound} The second sample uses the monofunctional compound 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidine (hereinafter referred to as "TMP-IEO"), which binds to the end of the polyester molecules.

Sample II.I-a

The dye-modifying compound THP-1EO becomes as follows produced: A 400 ml stainless steel bomb, cooled to -78 ° C., is mixed with 157 g of 2,2,6,6-tetramethyl-4-hydroxypiperidine loaded. The bomb is evacuated, filled with nitrogen at atmospheric pressure and evacuated again. Then the bomb is weighed and connected to an ethylene oxide supply with a hose. Ethylene oxide is passed into the bomb until the weight gain is 52g. Then the bomb is sealed and the connection to the ethylene oxide supply interrupted. The bomb is heated to 110 ° C for 1 hour, 120 ° C for 1 hour, 130 ° C for 1 hour and 4 hours Heated 155-160 ° C. The bomb is then cooled and 204 grams of product are discharged. This material will be used twice sublimed at 150 ° C and a pressure of less than 1 torr,

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DP-933

purified 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine (THP-1EO) is obtained as a white product which melts at 180-183 ° C.

0.90 g of THP-1E0 are mixed with 75.0 g of polytetramethylene terephthalate (4GT) melted in a test tube under nitrogen for 0.25 hours. The polyester is cooled into flakes cut, polymerized in the solid phase and spun from the melt into a 5-ply yarn. To get the yarn in To stretch two steps, it is revolving at 19 »8 m / min Feed rollers at 46 m / min over one pin heated to 85 ° C and at 59 m / min over a second pin heated to 73 ° C Pen passed and wound up at 57.6 m / min. Then the yarn is processed into a knitted fabric. Samples of the knitted fabric are according to the general methods described at the beginning of the examples under pressure at pH values of 3.0 and 6.0 colored. The colorations are satisfactory and have a dark blue at the lower pH and a dark blue at the higher pH value a medium blue shade.

Sample III-b

The dye-modifying compound TMP-1E0 is after using the same procedure described in Example 2 for the first part of the preparation of TMP-20E0 is. Then the modified polyester is made by adding 75 g of polyethylene terephthalate / adipate oopolyester (the 5.5 percent by weight of adipate units) in the test tube with 1.05 g of TMP-1E0 in the melt. After doing that Mixture has been added to the test tube, the test tube is purged with nitrogen and evacuated, and this filling with nitrogen and evacuation is repeated four times. Then the contents are heated to 255 ° C under nitrogen until they reach melted, and stirred for 0.5 hour and then stirred for 1 hour at a pressure of not more than 1 torr. The polyester is cooled, cut into flakes, polymerized in the solid phase and spun into a 5-ply yarn,

- 35 40981 3/1097

which is wound up at a speed of 30.5 m / min. To draw this yarn, it is fed by the feed rollers rotating at 15.3 m / min over a pin heated to 85 ° C passed to a forging roll rotating at 68.6 m / min and then wound up at 67.7 m / min. Then the yarn becomes too a knitted fabric and the samples are processed at pH 3 according to the general procedures described above on the one hand in a dye liquor at atmospheric pressure and on the other hand colored in a printing inking machine. The samples take on medium blue tones.

B is ρ ie 1

Filaments are produced from modified linear terephthalic acid polyesters in which 2,2,6,6-tetramethylpiperidine groups are bonded to the polyester molecules via aromatic amide groups. The following samples explain the use of three different dye-modifying compounds, namely of (a) 5- / £ D »2,2,6,6-pentamethyl-4-piperidinyl) sulfamoyl7 ~ isophthalic acid dimethyl ester, hereinafter referred to as" PMP sulfonamide a " (b) / T2,2,6,6-tetramethyl-4-piperidinyl) -sulfamoyl-7-fluorene-9,9-dipropionic acid dimethyl ester, hereinafter referred to as "TMP-sulfonamide b ^M , and (c) N- (2, 2,6,6-Tetramethyl-4-piperidinyl) -terephthalamic acid methyl ester, hereinafter referred to as "TMP-carbonamide". These dye-modifying compounds are prepared as follows:

(a) PMP sulfonamide a

A solution of 11.7 g of 3 »5-dicarbomethoxybenzenesulfonyl chloride in 40 ml of methylene chloride is in the course of 30 minutes to a solution of 6.8 g of 4-amino-1,2,2,6,6-pentarnethylpiperidine added dropwise in 50 ml of methylene chloride. The reaction is slightly exothermic and the reaction temperature becomes kept between 25 and 30 ° C with the help of a water bath. When added, a white precipitate of the hydrochloride forms. After stirring for 12 hours, the hydrochloride will through

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DP-933

Neutralized addition of aqueous potassium carbonate solution. Then the phases are separated. The methylene chloride phase is with dried anhydrous sodium sulfate and the solvent evaporated in vacuo. The white residue becomes from a mixture uracrystallized from ethanol and hexane, and 11.5 g of the dye-modifying compound are obtained in the form of white crystals that melt at 143-145 C.

(b) THP sulfonamide b

A solution of 8.5 g of 9,9-dicarbomethoxyethylfluorenylsulfonyl chloride in 30 ml of methylene chloride is added to a solution of 3.0 g of 4-amino-2,2,6,6-tetramethylpiperidine in 30 ml Methylene chloride was added dropwise. The reaction is slightly exothermic, and the reaction temperature is increased with the aid of a Water bath kept below 30 ° C. The addition comes to mind heavy white precipitate. After stirring for 12 hours, the hydrochloride is filtered off and washed with methylene chloride and dried. 10.4 g of product are obtained. A slurry of this hydrochloric acid salt in 200 ml of methanol is made neutralized by adding 0.95 g of sodium methylate, the free base going into solution. The methanol is under vacuum stripped off and the residue is made into an aqueous slurry. The product is filtered off and dried and recrystallized from a mixture of ethyl acetate and hexane. 7.5 g of dye-modifying agents are obtained Compound in the form of white crystals that melt at 130-132 ° G.

(c) TMP carbonamide

A 500 ml round bottom flask is filled with 10.6 g of p-Oarbomethoxybenzoylchlorid and charged 80 ml of trichloromethane. A solution of 7.8 g of 4-amino-2,2,6,6-tetramethylpiperidine and 2 g NaOH in 60 ml of water was added. The mixture is stirred vigorously at room temperature for 2 hours and then filtered. The precipitation, which consists of the desired compound is recrystallized from dichloromethane and dried in a vacuum oven.

- 37 409813/1097

net. The dry sample melts at 138-139 ° C.

For the production of modified polyester threads, each one of the three dye-modifying compounds described above the general procedures described above are used. To store the "PMP-sulfonamide a" in the polyethylene terephthalate / adipate copolyester (2GT / 6) (5 »5 percent by weight adipate units) for the 'sample IV-a you yourself, the melt blending process. By storage from "TMP-sulfonamide b" in the same copolyester is obtained the sample IV-b. By embedding "TMP-Carbonamide" in Polyethylene terephthalate (homopolyester) is obtained as sample IV-c. The mixing in the melt is followed by the Polymerization in the solid phase, whereupon the products are cut into flakes and from the melt into 5-ply yarns spun. The yarns of samples IV-a and IV ~ b are then stretched in the same way as sample II-e of example 2. The sample IV-c is stretched in the same way as sample II-c of example 2. The yarns of samples IV-a and IV-c become two-sided Yarns plied. The samples of each of the yarns are dyed under pressure at pH values of 3> 0 and 4.5, respectively. Samples IV-a and IV-b take on a dark blue hue. Sample IV-c takes on staining at pH 3.0 a medium blue shade and when dyeing at a pH value of 4 | 5 a light blue shade.

A summary of the working conditions and properties the products of this and the next example are given in Table IV.

Example 5

There are threads made of a polyethylene terephthalate / adipate-Cppolyester (2GT / 6) containing 5.5 percent by weight of adipate units and with a 2,2,6,6-tetramethylpiperidine compound is modified, the amino-s-

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DP-933 * ^{H υ} ^ ^H

triazine bridges. The dye modifying compound is 2,2 '- ^, 6-bis - (^, 2j6,6-tetramethyl-4-piperidinyl7-amino) -s-triazin-2-ylimino / ^P -diethanol, which is prepared as follows: Ein 300 A ml round bottom flask is filled with 6.3 g of 2,4-dichloro-6-N-di- (2-hydroxyethyl) -amino-s-triazine, 100 ml of dioxane and 7.8 g of 4-amino-2,2,6 , 6-tetramethylpiperidine charged. The contents of the flask are heated to reflux temperature for 1 hour and then filtered. The white crystals are dissolved in water, whereupon excess NaOH is added. White crystals of the desired dye-modifying compound separate out. These crystals are filtered off and washed with water. They melt at 121-122 ° C. The dye-modifying compound is then incorporated into the 2GT / 6 copolyester by mixing in the melt in a test tube. This is followed by polymerization in the solid phase and melt spinning to form a 5-ply yarn. The yarn is drawn 2.0 times in a single stage on a pen heated to 85 ° C. The drawn yarn is laid into strands and samples of the strands are dyed in the print dyeing device at pH values of 3> 0 and 4.5. Satisfactory colored strands of dark blue color are obtained. All of the procedures in this example are followed, as are the general procedures described at the beginning of the examples. Details of the variables are given in Table IV.

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DP-933

Tabel

Example 1 - Sample no. Direct Ties I-c Unmodified polyester I-a I-b polyester 2GT / 6 RV * 2GT 2GT / 6 26.0 Modifiers 46.9 39.8 PHP Modified polyester THP THP Melt Mix Temperature, C 285 SSP **, h / temp., ⁰ G 285 285 - RV 96/180 58 / 180-190 . - $ N in dye 19.9 - reception centers 0.05 Modifier sharing 0.11 0.06 —Finally

Spinning and drawing

Spinneret temperature ^{, 0 C}
Number of threads
Recky relationship

Yarn properties

Total titer den
Strength, g / den
Fracture thinning,%
RV

To dye

method
Carrier, fi owf
Dye, $> owf
pH

248

4.6

195

3.4

18.7

40

3.5

272 34

3.3

62

5.1 30

22.4

-Print- 40 4 3; 5; 6

273

34

4.6

150

3.0

37

14.3

20 4 4; 5; 6; 7

* RV = relative viscosity
** SSP = solid phase polymerization

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DP-933

«Μ

Tabel

II

Example 2 - Oxyalkylene Linkages

Rehearsal Fr.

II-o

TTn-modified polyester

polyester
RV * 2GT / 6 • 2GT / 6 2GT / 6
27.6 260
5
4.0 Modifiers THP-20E0 ⁰ C ~
16/200
17.7
0.057
In the chain PHP-20E0 TMP-20B0 Modified polyester 28
2.8
7th
36.1 Melt mixing temperature _t
SSP **, h / temp .., ⁰ G
RV
i> H in dye
receiving parts
Modifier
position 249
14th
5.6 265-270
54/210 120/190
21.2
0.077 0.075
Terminally Spinning and drawing pressure
15th
2
3 Spinneret Temp., G
Number of threads
Stretching ratio 275
51
14.4 269-274
10
3.5 Yarn properties Total titer den
Strength, g / den
Elongation at break, #
RV --Boiling " ¹ "
10
3
4.5 strand
2.0
38
19.3 To dye method
Carrier, $> owf
Dye, $ owf
pH )
0
2
3

* RV = relative viscosity ** SSP = ■ Fe'stphasepolymerisation +) Dye liquor boils at room temperature

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409813/1097

DP-933

Sample no.

Table II ('continued)

Il-d

Il-e

Unmodified polyester

polyester ·. 2GO? 2GT / 6 15th 2GT / 6 RV * Carrier, i » owF 47 27.6 2 27.6 Modifiers Dye,% owf PHP-1OEO PHP-2OPO 3 PHP-5EO- pH 5P0 Modified polyester Melt Mixing Rap., C 288 265-270 265-270 SSP **, h / temp., ⁰ C - 120/190 120/190 RT - - - ^ N in dye • pick up 0.060 0.075 0.085 Modifier steepness Spinning and drawing Spinneret temp., ⁰ C Number of threads 274 260 262 Stretching ratio 34 5 5 Yarn properties 4.5 4.5 4.5 Total titer den Strength, g / den 151 38 16 Elongation at break, tfo 3.4 3.2 3.8 RV 29 45 18th To dye 14.5 24.5 23.4 method pressure Boiling ^{+ J} and pressure 50 15th 4th 2 3 * 5 3 | 4.5

* RV = relative viscosity
** SSP = solid phase polymerization
+) Dye liquor boils at room temperature

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4098 13/1097

Tabel

III

Example 3 Sample no. Alkylene bonds III-b Unmodified polyester III-a polyester 2GT / 6 RV * 4GT 30.8 Modifiers 51.3 TMP-IEO Modified polyester THP-1E0 Melt Mix Temp., C 255 SSP **, h / temp., ⁰ C 255 160/190 RV 144/190 33.6 i » N in paraffin - receiving parts 0.11 Modifier sharing 0.095 Terminally Spinning and drawing In the chain Spinneret Temp., C 264 Number of threads 232 5 Stretching ratio 5 4.5 Yarn properties 3.0 Total titer den 46 Strength, g / den 41 3.1 Fractional thinning, i ° 1.1 27 RV 82 - - To dye 16.9 method Boiling ' ¹ *', pressure Carrier, $ owP pressure 15th Dye, $ owf 15th 2 pH ■ 2 3 3.6

* RV = relative viscosity
** SSP = plague phase polymerization +) dye liquor boils at room temperature

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DP-953

Tabel

IV

Examples 4 and 5 Aromatic amide bonds and aroino-s-triazine compounds

example
Sample Kr.

It modifies polyester

polyester
RV *

Modifiers

Modified polyester Schmelzmischtemp., ⁰ C SSP **, h / Temp., C ⁰ RV

tfo N in dye uptake parts

Modifier sharing Spinning and drawing

Spinneret temperature, number of threads stretching ratio

Yarn properties

Total titre, strength, g / elongation at break, fo

To dye

method
Carrier, <fo owf dye, <fo owf pH

4th
IV-a 4th
IV-b 2GT / fi
, 19.5
PMP-SuIfon-
amide a 2GT / 6
19.5
TMP-SuIfon-
amide b 255
115/190
14.0 255
. 115/130
27.5 0.15
In the chain 0.084
In the chain
.- «τ 256
5
4.5 261
5
4.5 52
2.2
41 28
2.9
25th pressure
15th
2
3, O; 4.5 pressure
15th
2
5.0: 4.5

* RV = relative viscosity ** SSP = solid phase polymerization

- 44 - 409813/109 ?.

23W34. example (Continuation) 5 Table IV Sample no. 4th Unmodified polyester
polyester
RV * IV-c 2GT / 6
30.8 Modifiers 2GT
23.5 TMP amino
s-triazine Modified polyester
Melt Mix Temp., C
SSP **, h / temp ,, ⁰ C
RV
^ H in dye
on take off
Modifier middle position TMP carbon
amide 255
190/190
12.2
0.21
In the chain Spinning and drawing
Spinneret Cent., C
Number of threads
Stretching ratio 283
0
16.7
0.060
Terminally 245
5
2.0 Game characteristics
Total titer den
Strength, g / den
Elongation at break, $> 278
4.0 - " To dye
method
Carrier, fs owf
Dye- $ owf
pH 17th
2.3
44 Bridge
t5
2
3.0-4.5 pressure
15th
2
3.0

* RV == relative viscosity ** SSP = solid phase polymerization

- 45 4Q98 13/109?

Claims (2)

EGG. du Pont de Nemours September 17, 19 and Company DP-933 P atent Claims. 1. Textile fibers or threads that can be dyed with acid dyes a linear terephthalic acid polyester, with the basic Piperidine groups are bound to the polyester molecules, characterized in that 2,2,6,6-tetramethylpiperidine groups to the polyester molecules directly at their positions no. 1 and / or no. 4 or via oxyalkylene, alkylene, aromatic amide or amino-s-triazine groups are bonded. 2. Process for dyeing textile fibers or threads made from linear terephthalic acid polyesters in which basic piperidine groups are bound to the polyester molecules, with acid dyes, characterized in that the Piperidine groups are 2,2,6,6-tetramethylpiperidine groups and the fibers or threads are dyed in an acidic dye liquor. - 46 - 40-9813 / 1097